JMZ-5 and JMZ-6, ZEOLITES HAVING AN SZR-TYPE CRYSTAL STRUCTURE, AND METHODS OF THEIR PREPARATION AND USE

ABSTRACT

JMZ-5, an aluminosilicate having an SZR framework type and a sea-urchin type morphology is described. A calcined product, JMZ-5C, formed from JMZ-5 is also described. JMZ-6, an aluminosilicate having an SZR framework type and a needle, aggregate morphology is described. A calcined product, JMZ-6C, formed from JMZ-6 is also described. Methods of preparing these zeolites and their metal-containing calcined counterparts are described along with methods of using these zeolites and their metal containing calcined counterparts in treating exhaust gases.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. ProvisionalApplication No. 62/385,288, filed on Sep. 9, 2016, which is incorporatedherein by reference.

FIELD OF INVENTION

The present invention relates to JMZ-5, an aluminosilicate molecularsieve having an SZR-type structure and a sea urchin type morphology, anda calcined product (JMZ-5C) formed from JMZ-5. The present inventionalso relates to JMZ-6, an aluminosilicate molecular sieve having anSZR-type crystal structure and needle-aggregate-type morphology, and acalcined product (JMZ-6C) formed from JMZ-6. The invention also relatesto compositions and article comprising these materials, methods of theirpreparation and methods of their use as catalysts.

BACKGROUND OF THE INVENTION

Zeolites are crystalline or quasi-crystalline aluminosilicatesconstructed of repeating TO₄ tetrahedral units with T being mostcommonly Si, Al or P (or combinations of tetrahedral units). These unitsare linked together to form frameworks having regular intra-crystallinecavities and/or channels of molecular dimensions. Numerous types ofsynthetic zeolites have been synthesized and each has a unique frameworkbased on the specific arrangement of the tetrahedral units. Byconvention, each topological type is assigned a unique three-letter code(e.g., “SZR”) by the International Zeolite Association (IZA).

Zeolites have numerous industrial applications, and zeolites of certainframeworks, such as CHA, are known to be effective catalyst for treatingcombustion exhaust gas in industrial applications including internalcombustion engines, gas turbines, coal-fired power plants, and the like.In one example, nitrogen oxides (NO_(x)) in the exhaust gas may becontrolled through a so-called selective catalytic reduction (SCR)process whereby NO_(x) compounds in the exhaust gas are contacted with areducing agent in the presence of a zeolite catalyst.

Synthetic zeolites of the SZR topological type when prepared asaluminosilicate compositions are produced using structure-directingagents (SDAs), also referred to as a “templates” or “templating agents”.The SDAs that are used in the preparation of aluminosilicate SZRtopological-type materials are typically complex organic molecules,which guide or direct the molecular shape and pattern of the zeolite'sframework.

Generally, the SDA can be considered as a mold around which the zeolitecrystals form. After the crystals are formed, the SDA is removed fromthe interior structure of the crystals, usually by heating in air,leaving a molecularly porous aluminosilicate material.

SUZ-4 zeolite was first reported by S.A. Barri, U.S. Pat. No. 5,118,483(1992). In typical synthesis techniques ((1) Gao, S.; Wang, X.; Chu, W.The first study on the synthesis of uniform SUZ-4 zeolite nanofiber.Microporous and Mesoporous Materials 2012, 159, 105-110; (2) Gao, S.;Wang, X.; Wang, X.; Bai, Y. Green synthesis of SUZ-4 zeolitecontrollable in morphology and SiO2/Al₂O₃ ratio. Microporous andMesoporous Materials 2013, 174, 108-116; and (3) Vongvoradit, P.;Worathanakul, P. Fast Crystallization of SUZ-4 Zeolite with HydrothermalSynthesis: Part I Temperature and Time Effect. Procedia Engineering2012, 32, 198-204), solid zeolite crystals precipitate from a reactionmixture which contains the framework components (e.g., a source ofsilica and a source of alumina), a source of hydroxide ions (e.g., NaOHor KOH), and an SDA. Such synthesis techniques usually take several days(depending on factors such as crystallization temperature) to achievethe desired crystallization. When crystallization is complete, the solidprecipitate containing the zeolite crystals is separated from the motherliquor, which is discarded. This discarded mother liquor contains unusedSDA, which is often degraded, and unreacted silica.

SUZ-4 has a needle-shaped morphology. (Lawton, S.L., Bennett, J.M.,Schlenker, J.L. and Rubin, M.K., Synthesis and proposed frameworktopology of zeolite SUZ-4, Chem. Commun., 894-896 (1993)) and(Strohmaier, K.G., Afeworki, M. and Dorset, D.L., The crystal structuresof polymorphic SUZ-4, Z. Kristallogr., 221, 689-698 (2006)).

Concerns have been raised about the use of aluminosilicates havingneedle-like morphology due to similarities with asbestosis. For example,erionite is a natural zeolite having an ERI framework type. Themorphology of erionite has been classified as being: single crystals ashexagonal prisms terminated by a pinacoid with sizes under 3 mm. (IZACommission on Natural Zeolites). It has been shown that exposure toerionite can result in a potential health hazard because, compared toother mineral particles, erionite has been shown to have greaterpathogenicity than asbestos. (Michele Mattioli, Matteo Giordani, MeralDogan, Michela Cangiotti, Giuseppe Avella, Rodorico Giorgi A. UmranDogan, and Maria Francesca Ottaviani; Morpho-chemical characterizationand surface properties of carcinogenic zeolite fibers; Journal ofHazardous Materials 306 (2016) 140-148) (Elizabeth A.Oczypok, Matthew S.Sanchez, Drew R. Van Orden, Gerald J. Berry, Kristina Pourtabib, MickeyE. Gunter, Victor L. Roggli, Alyssa M. Kraynie, and Tim D. Oury;Erionite-associated malignant pleural mesothelioma in Mexico; Int J ClinExp Pathol 2016; 9(5):5722-5732.)

One potential method to address concerns related to the morphology of analuminosilicate having a specific framework type is to develop a formhaving a different morphology while maintaining the same framework type.(U.S. Pat. No. 5,961,951A; Kennedy, C.L.; Rollmann, L.D.; Schlenker,J.L. Synthesis ZSM-48. 1999.) (U.S. Pat. No. 6,923,949 B1; Lai, W.F.;Saunders, R.B.; Mertens, M.M.; Verduijn, J.P. Synthesis of ZSM-48crystals with heterostructural, non ZSM-48, seeding. 2005)

There is a need to develop new zeolites having the basic structure ofknown zeolites, where minor changes in the product morphology can affectone or more of the properties of the zeolite. In some cases, while minorchanges in the morphology may not be discernable using commonly usedanalytical techniques, the catalytic activity of the structurally (andhere) modified zeolite may be improved relative to very closely relatedanalogous zeolites. Unexpected improvements in the catalytic activity ofsuch morphologically modified zeolites can allow for the compositions ofexhaust gases from engines to meet various regulatory requirements.

SUMMARY OF THE INVENTION

In a first aspect of the invention, provided is a novel zeolite, JMZ-5,an aluminosilicate comprising a SZR structure and having an acicular,also referred to as a sea-urchin, type morphology.

In a second aspect of the invention, provided is a calcined product(JMZ-5C) formed from JMZ-5.

In a third aspect of the invention, provided is a novel zeolite, JMZ-6,an aluminosilicate comprising a SZR structure and having aneedle-aggregate type morphology.

In a fourth aspect of the invention, provided is a calcined product(JMZ-6C) formed from JMZ-6.

In a fifth aspect of the invention, provided are catalytic compositionscomprising JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C, a metalimpregnated JMZ-6C, or a mixture thereof.

In a sixth aspect of the invention, provided are articles comprisingJMZ-5C, a metal impregnated JMZ-5C, JMZ-6C, a metal impregnated JMZ-6Cor a mixture thereof.

In a seventh aspect of the invention, provided is a method for formingJMZ-5 by using faujasite as a source of silica and aluminum in thereaction mixture used to form JMZ-5.

In an eighth aspect of the invention, provided is a method for formingJMZ-5 by using specific calcined seeds in the reaction mixture used toform JMZ-5.

In a ninth aspect of the invention, provided is a method for formingJMZ-6 by using specific as-made seeds in the reaction mixture used toform JMZ-6.

In a tenth aspect of the invention, provided is a method for formingJMZ-5C by calcining JMZ-5 or forming JMZ-6C by calcining JMZ-6.

In an eleventh aspect of the invention, provided is a method fortreating an exhaust gas from an engine by contacting the exhaust gaswith one or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or ametal impregnated JMZ-6C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an SEM showing the acicular, also referred to as a sea urchin,morphology of JMZ-5.

FIG. 2 is an SEM showing the needle aggregate morphology of JMZ-6.

FIG. 3 is an XRD pattern of samples of as-made and calcined SZR, asprepared in Example 1.

FIG. 4 is an SEM of a calcined sample of SZR, as prepared in Example 1.

FIG. 5 is an SEM of a sample of FAU used as the silicon and aluminumsource in preparing JMZ-5 as described in Example 2.

FIG. 6 is an XRD pattern of samples of as-made and calcined JMZ-5prepared using FAU as the Si and Al source as described in Example 2.

FIG. 7 is an SEM of a sample of calcined JMZ-5 prepared using FAU as theSi and Al source as described in Example 2.

FIG. 8 is an SEM of a sample of CHA used as seeds in preparing JMZ-5 asdescribed in Example 3.

FIG. 9 is an SEM of calcined JMZ-5 made using CHA seeds as described inExample 3.

FIG. 10 is an XRD pattern of as-made and calcined JMZ-5 made using CHAseeds as described in Example 3.

FIG. 11 is a graph of the XRD pattern of SZR, JMZ-5 made using FAU asthe silicon and aluminum source, and JMZ-5 made using CHA seeds, as thecrystal morphology corresponding to each of these materials.

FIG. 12 is an SEM of calcined pure silica CHA seeds as described inExample 4.

FIG. 13 is an XRD pattern of as-made and calcined JMZ-5 made using CHAseeds as described in Example 4.

FIG. 14 is an SEM of calcined JMZ-5 prepared with calcined pure silicaCHA seeds as described in Example 4.

FIG. 15 is an XRD pattern of amorphous material made using FAU seeds asdescribed in Example 5.

FIG. 16 is an XRD pattern of material having a BEA structure made fromthe reaction mixture using as-made boron BEA seeds as described inExample 6.

FIG. 17 is an XRD pattern of as-made and calcined material having a BEAstructure made from the reaction mixture using calcined aluminosilicatebeta-zeolite (BEA) seeds as described in Example 7.

FIG. 18 is an XRD pattern of SZR made with as-made pure silica LTA seedsas described in Example 8.

FIG. 19 is an SEM of calcined SZR made with as-made pure silica LTAseeds as described in Example 8.

FIG. 20 is an XRD pattern of as-made JMZ-5 made with calcined puresilica LTA seeds as described in Example 9.

FIG. 21 is an SEM of calcined JMZ-5 made using calcined pure silica LTAseeds as described in Example 9.

FIG. 22 is an XRD pattern of JMZ-6 made with as-made aluminosilicate LTAseeds as described in Example 10.

FIG. 23 is an SEM of calcined JMZ-6 made with as-made aluminosilicateLTA seeds as described in Example 10.

FIG. 24 is an XRD pattern of JMZ-5 made with calcined aluminosilicateLTA seeds as described in Example 11.

FIG. 25 is an SEM of calcined JMZ-5 made with calcined aluminosilicateLTA seeds as described in Example 11.

FIG. 26 is a graph showing the % NOx conversion of fresh JMZ-5 madeusing FAU seeds and CHA seeds, with Cu-CHA and BEA as described inExample 12.

FIG. 27 is a graph showing the % NOx conversion of aged JMZ-5 made usingFAU seeds and CHA seeds, with Cu-CHA and BEA as described in Example 12.

FIG. 28 is a graph showing the % N₂O conversion of fresh JMZ-5 madeusing FAU seeds and CHA seeds, with Cu-CHA and BEA as described inExample 12.

FIG. 29 is a graph showing the % N₂O conversion of aged JMZ-5 made usingFAU seeds and CHA seeds, with Cu-CHA and BEA as described in Example 12.

DETAILED DESCRIPTION OF THE INVENTION

As used in this specification and the appended claims, the singularforms “a”, “an” and “the” include plural referents unless the contextclearly indicates otherwise. Thus, for example, reference to “acatalyst” includes a mixture of two or more catalysts, and the like.

The term “SZR” refers to an SZR topological type as recognized by theInternational Zeolite Association (IZA) Structure Commission. The term“comprising an SZR type framework” means the material having a primarycrystalline phase that is SZR. Other crystalline phases may also bepresent, but the primary crystalline phase comprises at least about 90weight percent SZR, preferably at least about 95 weight percent SZR, andeven more preferably at least about 97 or at least about 99 weightpercent SZR. Preferably, the SZR molecular sieve is substantially freeof other crystalline phases and is not an intergrowth of two or moreframework types. By “substantially free” with respect to othercrystalline phases, it is meant that the molecular sieve contains atleast 99 weight percent SZR.

The terms “BEA”, “CHA” and “LTA” refer to topological types betazeolite, chabazite and zeolite A (also known as Linde Type A),respectively.

The term “calcine”, or “calcination”, means heating the material in air,oxygen or an inert atmosphere. Calcination is performed to decompose ametal salt, promote the exchange of metal ions within the catalyst, toadhere the catalyst to a substrate and to remove the SDA from themicropores of the materials prepared herein.

The term “about” means approximately and refers to a range that isoptionally ±25%, preferably ±10%, more preferably, ±5%, or mostpreferably ±1% of the value with which the term is associated.

When a range, or ranges, for various numerical elements are provided,the range, or ranges, can include the values, unless otherwisespecified.

The term “acicular”, also referred to as “sea urchin” means that aplurality of needle-shaped crystals having two ends are joined togetherat only one of the ends in a central location. This type of morphologycan also be described as a bundle of radiating needles. An SEM of JMZ-5showing the sea urchin shape is shown in FIG. 1, where small needlesgrow out of a spherical core with approximately radial directions.

The term “needle aggregate” refers to clusters of needle-like crystalsthat extend in multiple directions and do not radiate from a centralarea. An SEM of JMZ-5 showing the needle aggregate shape is shown inFIG. 2 where the needles are observed to be present in a variety ofdirections but do not emanate from a central area.

As used herein the term “zeolite” means an aluminosilicate molecularsieve having a framework constructed of alumina and silica (i.e.,repeating SiO₄ and AlO₄ tetrahedral units). Under special synthesisconditions, zeolites can be ‘siliceous’ meaning that aluminum is onlypresent as an impurity.

The zeolites of the present invention are not silicoaluminophosphates(SAPOs) and thus do not have an appreciable amount of phosphorous intheir framework. That is, the zeolite frameworks do not have phosphorousas a regular repeating unit and/or do not have an amount of phosphorousthat would affect the basic physical and/or chemical properties of thematerial, particularly with respect to the material's capacity toselectively reduce NO_(x) over a broad temperature range. The amount offramework phosphorous can be less than about 1 weight percent,preferably less than 0.1 weight percent, most preferably less than 0.01weight percent, based on the total weight of the zeolite.

Zeolites, as used herein, are free or substantially free of frameworkatoms or T-atoms, other than silicon and aluminum. Thus, a “zeolite” isdistinct from a “metal-substituted zeolite”, wherein the lattercomprises a framework that contains one or more non-aluminum metalssubstituted into the zeolite's framework. The zeolite framework, or thezeolite as a whole, can be free or essentially free of transitionmetals, including copper, nickel, zinc, iron, tungsten, molybdenum,cobalt, titanium, zirconium, manganese, chromium, vanadium, niobium, aswell as tin, bismuth, and antimony; is free or essentially free of noblemetals including platinum group metals (PGMs), such as ruthenium,rhodium, palladium, indium, platinum, and precious metals such as goldand silver; and is free or essentially free of rare earth metals such aslanthanum, cerium, praseodymium, neodymium, europium, terbium, erbium,ytterbium, and yttrium. The zeolites of the present invention maycontain low levels of iron: the iron may be in a framework tetrahedralsite and/or as a cationic species. The amount of iron in a frameworktetrahedral site and/or as a cationic species following synthesis isusually less than about 0.1 weight percent.

In a first aspect of the invention, provided is a novel zeolite, JMZ-5,an aluminosilicate comprising a SZR type framework structure and havinga sea-urchin type morphology.

JMZ-5 has an X-ray powder diffraction pattern substantially similar tothat of an SZR type framework. “Substantially similar” means thepatterns are qualitatively the same with regard to the locations of thepeaks. One skilled in the art would be able to determine if twomaterials have similar X-ray diffraction patterns.

JMZ-5 can have a silica to alumina ratio (SAR) of 15 to 40, preferably15 to 32, more preferably 15 to 25, even more preferably 15 to 20.

JMZ-5 further comprises a structure-directing agent. Preferably thestructure-directing agent comprises tetraethylammonium cations, N′, N′,N′, N′, N′, N′-hexaethylpentanediammonium cations or quinuclidine. Whentetraethylammonium cations are being used, the absence or near absenceof Na⁺ in the synthesis mixture has been reported to be important forSUZ-4 crystallization to proceed in the TEA⁺ system” (Amit C. Gujar,Geoffrey L. Price; Synthesis of SUZ-4 in the K+/TEA+ system. 2002).

In a second aspect of the invention, provided is a calcined product(JMZ-5C) formed from JMZ-5.

JMZ-5C is a calcined aluminosilicate molecular sieve comprising a SZRtype framework and having a sea-urchin type crystal morphology. The XRDpattern of the

JMZ-5C is similar to other zeolites having an SZR type structure.

JMZ-5C is useful as a catalyst in certain applications. Dried JMZ-5crystals are preferably calcined, but can also be used withoutcalcination.

JMZ-5C can be used either without a post-synthesis metal exchange orwith a post-synthesis metal exchange, preferably with a post-synthesismetal exchange.

JMZ-5C can be free or essentially free of any exchanged metal,particularly post-synthesis exchanged or impregnated metals.

JMZ-5C can further comprise one or more catalytic metal ions exchangedor otherwise impregnated into the channels and/or cavities of thezeolite. A metal in these positions are also known as extra-frameworkmetal cations. The extra-framework metal cation can be an alkali metalcation, an alkaline earth metal cation, a transition metal cation or amixture thereof.

Examples of metals that can be post-zeolite synthesis exchanged orimpregnated include transition metals, including copper, nickel, zinc,iron, tungsten, molybdenum, cobalt, titanium, zirconium, manganese,chromium, vanadium, niobium, as well as the main group metals tin,bismuth, and antimony; noble metals including platinum group metals(PGMs), such as ruthenium, rhodium, palladium, indium, platinum, andprecious metals such as gold and silver; alkaline earth metals such asbarium, beryllium, calcium, magnesium, and strontium; and rare earthmetals such as cerium, erbium, europium, lanthanum, neodymium,praseodymium, terbium, ytterbium, and yttrium.

Preferably, the extra-framework metal comprises calcium, cerium, cobalt,copper, chromium, iron, lithium, manganese, nickel, potassium, sodium,strontium or a combination of two or more of these metals. Morepreferably, the extra-framework metal comprises copper, iron, manganeseor a combination of two or more of these metals.

These metals can be present in an amount of about 0.1 to about 10 weightpercent, for example about 0.5 to about 5 weigh percent, about 0.1 toabout 1.0 weight percent, about 2.5 to about 3.5 weight percent, andabout 4.5 to about 5.5 weight percent, wherein the weight percent isrelative to the total weight of the zeolite.

Particularly preferred exchanged metals include copper and iron,particularly when combined with calcium and/or cerium and particularlywhen the transition metals (T_(M)) and the alkaline metals (A_(M)) arepresent in a T_(M):A_(M) molar ratio of about 15:1 to about 1:1, forexample about 10:1 to about 2:1, about 10:1 to about 3:1, or about 6:1to about 4:1.

Metals incorporated post-synthesis can be added to the molecular sievevia any known technique such as ion exchange, impregnation, isomorphoussubstitution, etc.

These exchanged metal cations are distinct from metals constituting themolecular framework of the zeolite, and thus metal exchanged zeolitesare distinct from metal-substituted zeolites.

In a third aspect of the invention, provided is a novel zeolite, JMZ-6,an aluminosilicate comprising a SZR structure and havingneedle-aggregate type morphology.

JMZ-6 has an X-ray powder diffraction pattern substantially similar tothat of an SZR type framework.

JMZ-6 can have a silica to alumina ratio (SAR) of 10 to 30, preferably15 to 25, more preferably 15 to 20.

JMZ-6 further comprises a structure-directing agent. Preferably thestructure-directing agent comprises tetraethylammonium cations, N′, N′,N′, N′, N′, N′-hexaethylpentanediammonium cations or quinuclidine.

In a fourth aspect of the invention, provided is a calcined product(JMZ-6C) formed from JMZ-6.

JMZ-6C is a calcined aluminosilicate molecular sieve comprising a SZRtype framework and having sea-urchin type crystal morphology. The XRDpattern of the JMZ-6C is similar to other zeolites having an SZR typestructure.

JMZ-6C is useful as a catalyst in certain applications. Dried JMZ-6crystals are preferably calcined, but can also be used withoutcalcination.

JMZ-6C can be used either without a post-synthesis metal exchange orwith a post-synthesis metal exchange, preferably with a post-synthesismetal exchange.

JMZ-6C can be free or essentially free of any exchanged metal,particularly post-synthesis exchanged or impregnated metals.

JMZ-6C can further comprise one or more catalytic metal ions exchangedor otherwise impregnated into the channels and/or cavities of thezeolite as described above for JMZ-5C.

JMZ-6C can further comprise an extra-framework metal. Theextra-framework metal can be an alkali metal, an alkaline earth metal, atransition metal or a mixture thereof. Preferably, the extra-frameworkmetal comprises calcium, cerium, cobalt, copper, chromium, iron,lithium, manganese, nickel, potassium, sodium, strontium or acombination of two or more of these metals. More preferably, theextra-framework metal comprises copper, iron, manganese or a combinationof two of more of these metals.

In a fifth aspect of the invention, provided are catalytic compositionscomprising JMZ-5C, JMZ-6C, or a mixture thereof.

Catalytic composition comprise JMZ-5C, JMZ-6C, or a mixture thereof, andone or more supports, such as alumina, a zeolite such as analuminosilicate zeolite, silica, non-zeolite silica alumina, ceria,zirconia, titania or a mixed or composite oxide containing both ceriaand zirconia.

One or more additional materials, such as fillers, binders, stabilizers,rheology modifiers, and other additives, can also be present in thecomposition.

The catalyst composition can comprise a catalyst comprising JMZ-5C,JMZ-6C, or a mixture thereof, where the catalyst comprises anextra-framework metal.

The extra-framework metal can be an alkali metal, an alkaline earthmetal, a transition metal or a mixture thereof. Preferably, theextra-framework transition metal comprises one or more of calcium,cerium, cobalt, copper, chromium, iron, lithium, manganese, molybdenum,nickel, niobium, potassium, sodium, strontium, tantalum, tungsten,vanadium or a combination of two or more of these metals

The extra-framework metal can comprise about 0.1 to about 10, preferablyabout 0.1 to about 5, weight percent of total weight of the molecularsieves, extra-framework metal and catalytically active metal in thecatalyst. Preferably, the molecular sieve comprises about 0.1 to about10, preferably about 0.1 to about 5, weight percent of copper, iron,manganese or a combination of two or more of these metals.

In a sixth aspect of the invention, provided are articles comprisingJMZ-5C, JMZ-6C, or a mixture thereof.

Catalysts of the present invention are particularly applicable forheterogeneous catalytic reaction systems (i.e., solid catalyst incontact with a gas reactant). To improve contact surface area,mechanical stability, and/or fluid flow characteristics, the catalystscan be disposed on and/or within a substrate, preferably a poroussubstrate. A washcoat containing the catalyst can be applied to an inertsubstrate, such as corrugated metal plate or a honeycomb cordieritebrick. Alternatively, the catalyst is kneaded along with othercomponents such as fillers, binders, and reinforcing agents, into anextrudable paste which is then extruded through a die to form ahoneycomb brick. Accordingly, a catalyst article can comprise an SZRcatalyst described herein coated on and/or incorporated into asubstrate.

Certain aspects of the invention provide a catalytic washcoat. Thewashcoat comprising a calcined product formed from JMZ-5 describedherein is preferably a solution, suspension, or slurry. Suitablecoatings include surface coatings, coatings that penetrate a portion ofthe substrate, coatings that permeate the substrate, or some combinationthereof.

A washcoat can also include non-catalytic components, such as fillers,binders, stabilizers, rheology modifiers, and other additives, includingone or more of alumina, silica, non-zeolite silica alumina, titania,zirconia, ceria. The catalyst composition can comprise pore-formingagents such as graphite, cellulose, starch, polyacrylate, andpolyethylene, and the like. These additional components do notnecessarily catalyze the desired reaction, but instead improve thecatalytic material's effectiveness, for example, by increasing itsoperating temperature range, increasing contact surface area of thecatalyst, increasing adherence of the catalyst to a substrate, etc.

The binder can comprise cerium or ceria. When the binder contains ceriumor ceria, the cerium containing particles in the binder are preferablysignificantly larger than the cerium containing particles in thecatalyst.

The amount of washcoat deposited on a substrate is referred to as thewashcoat loading. Preferably, the washcoat loading is >0.3 g/in³, suchas >1.2 g/in³, >1.5 g/in³, >1.7 g/in³ or >2.00 g/in³, and preferably<3.5 g/in³, such as <2.5 g/in³. The washcoat can be applied to asubstrate in a loading of about 0.8 to 1.0 g/in³, 1.0 to 1.5 g/in³, or1.5 to 2.5 g/in³.

Two of the most common substrate designs to which catalyst may beapplied are plate and honeycomb. Preferred substrates, particularly formobile applications, include flow-through monoliths having a so-calledhoneycomb geometry that comprise multiple adjacent, parallel channelsthat are open on both ends and generally extend from the inlet face tothe outlet face of the substrate and result in a high-surfacearea-to-volume ratio. For certain applications, the honeycombflow-through monolith preferably has a high cell density, for exampleabout 600 to 800 cells per square inch, and/or an average internal wallthickness of about 0.18-0.35 mm, preferably about 0.20-0.25 mm. Forcertain other applications, the honeycomb flow-through monolithpreferably has a low cell density of about 150-600 cells per squareinch, more preferably about 200-400 cells per square inch. Preferably,the honeycomb monoliths are porous. In addition to cordierite, siliconcarbide, silicon nitride, ceramic, and metal, other materials that canbe used for the substrate include aluminum nitride, aluminum titanate,a-alumina, mullite, e.g., acicular mullite, pollucite, a thermet such asAl₂OsZFe, Al₂O₃/Ni or B₄CZFe, or composites comprising segments of anytwo or more thereof. Preferred materials include cordierite, siliconcarbide, and alumina titanate. Plate-type catalysts have lower pressuredrops and are less susceptible to plugging and fouling than thehoneycomb types, which is advantageous in high efficiency stationaryapplications, but plate configurations can be much larger and moreexpensive. A honeycomb configuration is typically smaller than a platetype, which is an advantage in mobile applications, but has higherpressure drops and plug more easily. The plate substrate can beconstructed of metal, preferably corrugated metal.

A catalyst article can be made by a process described herein. Thecatalyst article can be produced by a process that includes the steps ofapplying one or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or ametal impregnated JMZ-6C, preferably as a washcoat, to a substrate as alayer either before or after at least one additional layer of anothercomposition for treating exhaust gas has been applied to the substrate.The one or more catalyst layers on the substrate, including the catalystlayer comprising one or more of JMZ-5C, a metal impregnated JMZ-5C,JMZ-6C or a metal impregnated JMZ-6C, are arranged in consecutivelayers. As used herein, the term “consecutive” with respect to catalystlayers on a substrate means that each layer is contact with its adjacentlayer(s) and that the catalyst layers as a whole are arranged one on topof another on the substrate.

One or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metalimpregnated JMZ-6C can be disposed on the substrate as a first layer orzone and another composition, such as an oxidation catalyst, reductioncatalyst, scavenging component, or NO_(x) storage component, can bedisposed on the substrate as a second layer or zone. As used herein, theterms “first layer” and “second layer” are used to describe the relativepositions of catalyst layers in the catalyst article with respect to thenormal direction of exhaust gas flow-through, past, and/or over thecatalyst article. Under normal exhaust gas flow conditions, exhaust gascontacts the first layer prior to contacting the second layer.

The second layer can be applied to an inert substrate as a bottom layerand the first layer is a top layer that is applied over the second layeras a consecutive series of sub-layers.

The exhaust gas can penetrate (and hence contact) the first layer,before contacting the second layer, and subsequently returns through thefirst layer to exit the catalyst component.

The first layer can be a first zone disposed on an upstream portion ofthe substrate and the second layer is disposed on the substrate as asecond zone, wherein the second zone is downstream of the first.

A catalyst article can be produced by a process that includes the stepsof applying one or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C ora metal impregnated JMZ-6C, preferably as a washcoat, to a substrate asa first zone, and subsequently applying at least one additionalcomposition for treating an exhaust gas to the substrate as a secondzone, wherein at least a portion of the first zone is downstream of thesecond zone. Alternatively, one or more of JMZ-5C, a metal impregnatedJMZ-5C, JMZ-6C or a metal impregnated JMZ-6C can be applied, preferablyas a washcoat, to the substrate in a second zone that is downstream of afirst zone containing the additional composition. Examples of additionalcompositions include oxidation catalysts, reduction catalysts,scavenging components (e.g., for sulfur, water, etc.), or NO_(x) storagecomponents.

To reduce the amount of space required for an exhaust system, individualexhaust components can be designed to perform more than one function.For example, applying an SCR catalyst to a wall-flow filter substrateinstead of a flow-through substrate serves to reduce the overall size ofan exhaust treatment system by allowing one substrate to serve twofunctions, namely catalytically reducing NO_(x) concentration in theexhaust gas and mechanically removing soot from the exhaust gas. Thesubstrate can be a honeycomb wall-flow filter or partial filter.Wall-flow filters are similar to flow-through honeycomb substrates inthat they contain a plurality of adjacent, parallel channels. However,the channels of flow-through honeycomb substrates are open at both ends,whereas the channels of wall-flow substrates have one end capped,wherein the capping occurs on opposite ends of adjacent channels in analternating pattern. Capping alternating ends of channels prevents thegas entering the inlet face of the substrate from flowing straightthrough the channel and exiting. Instead, the exhaust gas enters thefront of the substrate and travels into about half of the channels whereit is forced through the channel walls prior to entering the second halfof the channels and exiting the back face of the substrate.

The substrate wall has a porosity and pore size that is gas permeable,but traps a major portion of the particulate matter, such as soot, fromthe gas as the gas passes through the wall.

Porosity is a measure of the fraction of void space in a poroussubstrate and is related to backpressure in an exhaust system:generally, the lower the porosity, the higher the backpressure.Preferably, the porous substrate has a porosity of about 30 to about80%, for example about 40 to about 75%, about 40 to about 65%, or fromabout 50 to about 60%.

The pore interconnectivity, measured as a percentage of the substrate'stotal void volume, is the degree to which pores, void, and/or channels,are joined to form continuous paths through a porous substrate, i.e.,from the inlet face to the outlet face. In contrast to poreinterconnectivity is the sum of closed pore volume and the volume ofpores that have a conduit to only one of the surfaces of the substrate.Preferably, the porous substrate has a pore interconnectivity volume ofat least about 30%, more preferably at least about 40%.

The mean pore size of the porous substrate is also important forfiltration. Mean pore size can be determined by any acceptable means,including by mercury porosimetry. The mean pore size of the poroussubstrate should be of a high enough value to promote low backpressure,while providing an adequate efficiency by either the substrate per se,by promotion of a soot cake layer on the surface of the substrate, orcombination of both. Preferred porous substrates have a mean pore sizeof about 10 to about 40 μm, for example about 20 to about 30 μm, about10 to about 25 μm, about 10 to about 20 μm, about 20 to about 25 μm,about 10 to about 15 μm, and about 15 to about 20 μm.

Preferred wall-flow substrates are high efficiency filters. Wall flowfilters for use with the present invention preferably have an efficiencyof least 70%, at least about 75%, at least about 80%, or at least about90%. The efficiency can be from about 75 to about 99%, about 75 to about90%, about 80 to about 90%, or about 85 to about 95%. Here, efficiencyis relative to soot and other similarly sized particles and toparticulate concentrations typically found in conventional dieselexhaust gas. For example, particulates in diesel exhaust can range insize from 0.05 microns to 2.5 microns. Thus, the efficiency can be basedon this range or a sub-range, such as 0.1 to 0.25 microns, 0.25 to 1.25microns, or 1.25 to 2.5 microns.

In general, the production of an extruded solid body, such as honeycombflow-through or wall-flow filter, containing one or more of JMZ-5C, ametal impregnated JMZ-5C, JMZ-6C or a metal impregnated JMZ-6C involvesblending one or more of these material, a binder, an optional organicviscosity-enhancing compound into a homogeneous paste which is thenadded to a binder/matrix component or a precursor thereof and optionallyone or more of stabilized ceria, and inorganic fibers. The blend iscompacted in a mixing or kneading apparatus or an extruder. The mixtureshave organic additives such as binders, pore formers, plasticizers,surfactants, lubricants, dispersants as processing aids to enhancewetting and therefore produce a uniform batch. The resulting plasticmaterial is then molded, in particular using an extrusion press or anextruder including an extrusion die, and the resulting moldings aredried and calcined. The organic additives are “burnt out” duringcalcinations of the extruded solid body. JMZ-5C, a metal impregnatedJMZ-5C, JMZ-6C or a metal impregnated JMZ-6C may also be washcoated orotherwise applied to the extruded solid body as one or more sub-layersthat reside on the surface or penetrate wholly or partly into theextruded solid body.

The binder/matrix component is preferably selected from the groupconsisting of cordierite, nitrides, carbides, borides, intermetallics,lithium aluminosilicate, a spinel, an optionally doped alumina, a silicasource, titania, zirconia, titania-zirconia, zircon and mixtures of anytwo or more thereof. The paste can optionally contain reinforcinginorganic fibers selected from the group consisting of carbon fibers,glass fibers, metal fibers, boron fibers, alumina fibers, silica fibers,silica-alumina fibers, silicon carbide fibers, potassium titanatefibers, aluminum borate fibers and ceramic fibers.

The alumina binder/matrix component is preferably gamma alumina, but canbe any other transition alumina, i.e., alpha alumina, beta alumina, chialumina, eta alumina, rho alumina, kappa alumina, theta alumina, deltaalumina, lanthanum beta alumina and mixtures of any two or more suchtransition aluminas. It is preferred that the alumina is doped with atleast one non-aluminum element to increase the thermal stability of thealumina. Suitable alumina dopants include silicon, zirconium, barium,lanthanides and mixtures of any two or more thereof. Suitable lanthanidedopants include La, Ce, Nd, Pr, Gd and mixtures of any two or morethereof.

Preferably, one or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C ora metal impregnated JMZ-6C is dispersed throughout, and preferablyevenly throughout, the entire extruded catalyst body.

Where any of the above extruded solid bodies are made into a wall-flowfilter, the porosity of the wall-flow filter can be from 30-80%, such asfrom 40-70%. Porosity and pore volume and pore radius can be measurede.g. using mercury intrusion porosimetry.

The general procedures to forming JMZ-5 and JMZ-6 are described below

Methods for forming JMZ-5 and JMZ-6 use a structure-directing agent(SDA) comprising a tetraethylammonium cation as a structure-directingagent. The methods comprise the sequential steps of forming a reactionmixture and then reacting the mixture under hydrothermal conditions toform crystals containing the SDA and having an x-ray diffraction patternconsistent with that of SZR. The precipitated zeolite crystals arepreferably separated from the subsequent mother liquor by anyconventional technique, such as filtration.

JMZ-5 and JMZ-6 synthesized by the present methods may include one ormore non-framework alkali and/or alkaline earth metals. These metals aretypically introduced into the reaction mixture in conjunction with thesource of hydroxide ions. Examples of such metals include sodium and/orpotassium, and also magnesium, calcium, strontium, barium, lithium,cesium, and rubidium.

Usually it is desirable to remove the alkali metal cation by ionexchange and replace it with hydrogen, ammonium, or any desired metalion. Accordingly, zeolites of the present invention may be a Na-formzeolite, a K-form zeolite, or a combined N, K-form and the like, or maybe an H-form zeolite, an ammonium-form zeolite, or a metal-exchangedzeolite. Typical ion exchange techniques involve contacting thesynthetic zeolite with a solution containing a salt of the desiredreplacing cation or cations. Although a wide variety of salts can beemployed, chlorides and other halides, nitrates, sulfates and carbonatesare particularly preferred. Representative ion exchange techniques arewidely known in the art. Ion exchange occurs post-synthesis and can takeplace either before or after the zeolite is calcined. Following contactwith the salt solution of the desired replacing cation, the zeolite istypically washed with water and dried at temperatures ranging from 65°C. to about 315° C., usually between 80° C. and 150° C. After washing,the zeolite can be calcined in an inert gas and/or air at temperaturesranging from about 315° C. to 850° C. for periods of time ranging from 1to 48 hours, or more, to produce a catalytically active and stableproduct.

The reaction mixture used in the synthesis of JMZ-5 and JMZ-6 typicallycontains at least one source of silica, at least one source of alumina,at least one SDA useful in forming JMZ-5, and at least one source ofhydroxide ions. In one of the two methods for synthesizing JMZ-5,faujasite (FAU) is used as the sole or predominant source of silicon andaluminum.

Preferably, the overall process will have an overall yield on silica ofat least about 60%, for example at least about 70%, at least about 80%.Preferably, the overall process will have an overall yield on SDA of atleast about 40%, for example at least about 60%, at least about 80%, atleast about 90%, about 40-90%, about 40-60%, about 60-80%, about 80-90%,about 90-95%, or about 95-99%.

Suitable silica sources include, without limitation, fumed silica,silicates, precipitated silica, colloidal silica, silica gels, zeolitessuch as zeolite Y and/or zeolite X, and silicon hydroxides andalkoxides. Silica sources resulting in a high relative yield arepreferred.

Typical alumina sources also are generally known and include aluminates,alumina, other zeolites such as faujasite (FAU), aluminum colloids,boehmites, pseudo-boehmites, aluminum hydroxides, aluminum salts such asaluminum sulfate and alumina chloride, aluminum hydroxides andalkoxides, alumina gels, and aluminum metal in foil or powder form.

Typically, a source of hydroxide ions such as an alkali metal hydroxideand/or an alkaline earth metal hydroxide, including hydroxide of sodium,potassium, lithium, cesium, rubidium, calcium, and magnesium, is used inthe reaction mixture. However, this component can be omitted so long asthe equivalent basicity is maintained. The SDA can be used to providehydroxide ion. Thus, it may be beneficial to ion exchange, for example,the halide for hydroxide ion, thereby reducing or eliminating the alkalimetal hydroxide quantity required. The alkali metal cation or alkalineearth cation may be part of the as-synthesized crystalline oxidematerial, in order to balance valence electron charges therein.

Salts, particularly alkali metal halides such as sodium chloride, can beadded to or formed in the reaction mixture as well. Preferably, thereaction mixture is free or substantially free of fluorine,fluorine-containing compounds, and fluorine ions.

The reaction mixture can be in the form of a solution, a colloidaldispersion (colloidal sol), gel, or paste, with a gel being preferred.JMZ-5 can be prepared from a reaction mixture having the compositionshown in Table 2. Silicon- and aluminum-containing reactants areexpressed as SiO₂ and Al₂O₃, respectively.

TABLE 2 Typical Preferred SiO₂/Al₂O₃  10-100 15-60 OH⁻/SiO₂ 0.3-1.00.6-0.8 SDA/SiO₂ 0.05-0.50 0.10-0.20 Alkali metal cation/SiO₂ 0.10-1.0 0.15-0.35 H₂O/SiO₂ 10-80 15-40

Reaction temperatures, mixing times and speeds, and other processparameters that are suitable for conventional SZR synthesis techniquesare also generally suitable for the present invention. Generally, thereaction mixture is maintained at an elevated temperature until theJMZ-5 crystals are formed. The hydrothermal crystallization is usuallyconducted under autogenous pressure, at a temperature between about75-220° C., for example between about 120 and 160° C., for duration ofseveral hours, for example, about 0.1-20 days, and preferably from about0.25-3 days. Preferably, the zeolite is prepared using stirring oragitation.

During the hydrothermal crystallization step, when faujasite is used asthe source of silicon and aluminum, crystals of JMZ-5 can be used tofacilitate new crystals to nucleate spontaneously from the reactionmixture.

The use of JMZ-5 crystals as seed material can be advantageous indecreasing the time necessary for complete crystallization to occur andto minimize the formation of other crystalline impurities. When used asseeds, JMZ-5 crystals can be added in an amount between 0.1 and 10% ofthe weight of silica used in the reaction mixture.

When JMZ-5 is produced using non-SZR framework type crystals, or JMZ-6is produced, other seed crystal are used, as described below.

Once the JMZ-5 or JMZ-6 crystals have formed, the solid product isseparated from the reaction mixture by standard separation techniquessuch as filtration. The JMZ-5 or JMZ-6 crystals are water-washed andthen dried, for several second to a few minutes (e.g., 5 second to 10minutes for flash drying) or several hours (e.g., about 4-24 hours foroven drying at 75-150° C.), to obtain as-synthesized JMZ-5 or JMZ-6crystals having a SZR framework type material and SDA within thecrystals. The drying step can be performed at atmospheric pressure orunder vacuum.

It will be appreciated that the foregoing sequence of steps, as well aseach of the above-mentioned periods of time and temperature values aremerely exemplary and may be varied.

The JMZ-5 crystals produced in accordance with the methods describedherein can have a mean crystallite size of about 0.01 to about 5μm, forexample about 0.5 to about 5 μm, about 0.1 to about 1μm, and about 1 toabout 5μm. Large crystals can be milled using a jet mill or otherparticle-on-particle milling technique to an average size of about 1.0to about 1.5 micron to facilitate washcoating a slurry containing thecatalyst to a substrate, such as a flow-through monolith.

JMZ-5 synthesized by the methods described herein preferably have asilica-to-alumina ratio (SAR) of 15 to 40, preferably 20-32.

JMZ-6 synthesized by the methods described herein preferably have asilica-to-alumina ratio (SAR) of 10 to 30, preferably 15 to 25, morepreferably 15 to 20.

The SAR can be selectively achieved based on the composition of thestarting synthesis mixture and/or adjusting other process variables. Thesilica-to-alumina ratio of zeolites may be determined by conventionalanalysis. This ratio is meant to represent, as closely as possible, theratio in the rigid atomic framework of the zeolite crystal and toexclude silicon or aluminum in the binder (for catalyst applications)or, in cationic or other form, within the channels.

In a seventh aspect of the invention, provided is a method for formingJMZ-5 by using faujasite as a source of silica and aluminum in thereaction mixture used to form JMZ-5.

The method for synthesizing JMZ-5 can comprise:

-   -   a. forming a reaction mixture comprising: (a) a source of        silicon and aluminum, where the source of both silicon and        aluminum is an aluminosilicate molecular sieve having a non-SZR        type structure, and (b) a structure directing agent (SDA)        comprising a tetraethylammonium cation,    -   b. forming crystals comprising an SZR type framework and the        structure directing agent by hydrothermally aging the reaction        mixture formed in step a, and    -   c. recovering at least a portion of the molecular sieve crystals        from the mother liquor, where the molecular sieve crystals        comprise JMZ-5.

The source of silicon and/or aluminum can further comprise one or moreadditional components, wherein the one or more additional components arepresent in an amount such that at least 80% of the silicon and/oraluminum is provided by the aluminosilicate molecular sieve which doesnot have the SZR type structure.

The molecular sieve that is the source of alumina and silica is one ormore of faujasite (FAU), mordenite (MOR), zeolite P (GIS), and zeolite A(LTA).

The SDA can be associated with an anion selected from the groupconsisting of fluoride, chloride, bromide, iodide, hydroxide, acetate,sulfate, tetrafluoroborate, carboxylate, carbonate and bicarbonate, andnitrate.

The reaction mixture can be essentially free of fluoride.

The reaction mixture can further comprise a source of alkali metal (M),wherein the weight ratio of SiO₂: MOx (oxide of the alkali metal) isfrom 2 to 10, where M=Na, K, Ca, or Sr, and mixtures thereof.

The reaction mixture can further comprise a source of potassium.

The reaction mixture can be a gel having a molar compositional ratio of:

H₂O/SiO₂  10-100 OH/SiO₂ 0.01-1  R/SiO₂ 0.05-0.5 Al₂O₃/SiO₂ 0.01-0.1

wherein R is the SDA.

The invention also relates to a composition comprising the reactionmixture formed before hydrothermally treating the reaction mixture asdescribed in the methods of making JMZ-5.

In an eighth aspect of the invention, provided is a method for formingJMZ-5 by using specific calcined seeds in the reaction mixture used toform JMZ-5.

The method for synthesizing JMZ-5 comprises:

-   -   a. forming a reaction mixture comprising: (a) at least one        source of alumina, (b) at least one source of silica, and (c) a        structure directing agent (SDA) comprising tetraethylammonium        cations, N′, N′, N′, N′, N′, N′-hexaethylpentanediammonium        cations or quinuclidine.,    -   b. adding calcined aluminosilicate molecular sieve seed crystals        to the reaction mixture where the calcined aluminosilicate        molecular sieve seed crystals are a non-SZR type,    -   c. forming crystals comprising an SZR type framework and the        structure directing agent, and    -   d. recovering at least a portion of the molecular sieve crystals        from the mother liquor.

The calcined aluminosilicate molecular sieve seed crystals can compriseone or more of calcined Al-CHA, calcined Al-AEI, calcined Al-AFX,calcined silica LTA, and calcined Al-LTA.

The seeds crystals can be present in the reaction mixture from about 0.1to about 10% w/w of the total weight of the reaction mixture.

The seed crystals can comprise from 1 to 35 weight percent of at leastone crystalline molecular sieve impurity.

The invention also relates to a composition comprising the reactionmixture formed before hydrothermally treating the reaction mixture asdescribed in the methods of making JMZ-5.

In a ninth aspect of the invention, provided is a method for formingJMZ-6 by using as-made Al-LTA seeds in the reaction mixture used to formJMZ-6.

The method of forming JMZ-6 using specific as-made seeds in the reactionis the same as described above for forming JMZ-5 using non-SZR seeds,except that the seeds comprise an LTA type framework. A method forsynthesizing JMZ-6 can comprise the steps of:

-   -   a. forming a reaction mixture comprising: (a) at least one        source of alumina, (b) at least one source of silica, and (c) a        structure directing agent (SDA) comprising tetraethylammonium        cations, N′, N′, N′, N′, N′, N′-hexaethylpentanediammonium        cations or quinuclidine,    -   b. adding as-made aluminosilicate seed crystals having an LTA        type framework to the reaction mixture,    -   c. forming crystals comprising an SZR type framework and the        structure directing agent, and    -   d. recovering at least a portion of the molecular sieve crystals        from the mother liquor, where the molecular sieve crystals        comprise JMZ-6.

The seeds crystals can be present in the reaction mixture from about 0.1to about 10% w/w of the total weight of the reaction mixture.

The seed crystals can comprise from 1 to 35 weight percent of at leastone crystalline molecular sieve impurity.

The invention also relates to a composition comprising the reactionmixture formed before hydrothermally treating the reaction mixture asdescribed in the methods of making JMZ-6.

In a tenth aspect of the invention, provided is a method for formingJMZ-5C by calcining JMZ-5 or forming JMZ-6C by calcining JMZ-6.

JMZ-5 and JMZ-6 each contain a structure-directing agent (SDA), alsoknown as a template. The SDA can be removed by calcination, where JMZ-5or JMZ-6 is heated under an oxidizing atmosphere, such as air or oxygen,a neutral atmosphere, such as nitrogen or other inert gas, or a reducingatmosphere, such as hydrogen. The atmosphere can be dry or can includewater.

The temperatures used in calcination depend upon the components in thematerial to be calcined and generally are between about 400° C. to about900° C. for approximately 1 to 8 hours. In some cases, calcination canbe performed up to a temperature of about 1200° C. In applicationsinvolving the processes described herein, calcinations are generallyperformed at temperatures from about 400° C. to about 700° C. forapproximately 1 to 8 hours, preferably at temperatures from about 400°C. to about 650° C. for approximately 1 to 4 hours.

The samples may be heated to a desired temperature where the rate oftemperature change is constant or where the rate of temperature changeis not constant.

The samples can also be heated and maintained for a length of time attwo or more different temperatures, where the length of time the sampleis held at each temperature can be the same or different.

In an eleventh aspect of the invention, provided is a method fortreating an exhaust gas from an engine by contacting the exhaust gaswith one or more of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or ametal impregnated JMZ-6C and converting a portion of ammonia and NOx inan exhaust gas into nitrogen and water.

JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metal impregnated JMZ-6Ccan promote the reaction of a reductant, preferably ammonia, withnitrogen oxides to selectively form elemental nitrogen (N₂) and water(H₂O). Thus, the catalyst can be formulated to favor the reduction ofnitrogen oxides with a reductant (i.e., an SCR catalyst).

Examples of such reductants include hydrocarbons (e.g., C3-C6hydrocarbons) and nitrogenous reductants such as ammonia and ammoniahydrazine or any suitable ammonia precursor, such as urea ((NH₂)₂CO),ammonium carbonate, ammonium carbamate, ammonium hydrogen carbonate orammonium formate.

Preferably, JMZ-5C or JMZ-6C contains one or more metal ions, such ascopper, iron or manganese. The one more metals may be impregnated intoJMZ-5C or JMZ-6C. JMZ-5C, a metal containing JMZ-5C, JMZ-6 or a metalcontaining JMZ-6C can also promote the oxidation of ammonia.

The catalyst can be formulated to favor the oxidation of ammonia withoxygen, particularly a concentrations of ammonia typically encountereddownstream of an SCR catalyst (e.g., ammonia oxidation (AMOX) catalyst,such as an ammonia slip catalyst (ASC)). JMZ-5C, a metal impregnatedJMZ-5C, JMZ-6C or a metal impregnated JMZ-6C can be disposed as a toplayer over an oxidative under-layer, wherein the under-layer comprises aplatinum group metal (PGM) catalyst or a non-PGM catalyst. Preferably,the catalyst component in the underlayer is disposed on a high surfacearea support, including but not limited to alumina.

SCR and AMOX operations can be performed in series, wherein bothprocesses utilize a catalyst comprising the SZR catalyst describedherein, and wherein the SCR process occurs upstream of the AMOX process.For example, an SCR formulation of the catalyst can be disposed on theinlet side of a filter and an AMOX formulation of the catalyst can bedisposed on the outlet side of the filter.

Accordingly, provided is a method for the reduction of NO_(x) compoundsor oxidation of NH₃ in a gas, which comprises contacting the gas with acatalyst composition described herein for the catalytic reduction ofNO_(x) compounds for a time sufficient to reduce the level of NO_(x)compounds and/or NH₃ in the gas. A catalyst article can have an ammoniaslip catalyst disposed downstream of a selective catalytic reduction(SCR) catalyst. The ammonia slip catalyst can oxidize at least a portionof any nitrogenous reductant that is not consumed by the selectivecatalytic reduction process. The ammonia slip catalyst can be disposedon the outlet side of a wall flow filter and an SCR catalyst can bedisposed on the upstream side of a filter. The ammonia slip catalyst canbe disposed on the downstream end of a flow-through substrate and an SCRcatalyst can be disposed on the upstream end of the flow-throughsubstrate. The ammonia slip catalyst and SCR catalyst can be disposed onseparate bricks within the exhaust system. These separate bricks can beadjacent to, and in contact with, each other or separated by a specificdistance, provided that they are in fluid communication with each otherand provided that the SCR catalyst brick is disposed upstream of theammonia slip catalyst brick.

The SCR and/or AMOX process can be performed at a temperature of atleast 100° C., preferably at a temperature from about 150° C. to about750° C., more preferably from about 175 to about 550° C., even morepreferably from 175 to 400° C.

In some conditions, the temperature range can be from 450 to 900° C.,preferably 500 to 750° C., more preferably 500 to 650° C., even morepreferably 450 to 550° C. Temperatures greater than 450° C. areparticularly useful for treating exhaust gases from a heavy and lightduty diesel engine that is equipped with an exhaust system comprising(optionally catalyzed) diesel particulate filters which are regeneratedactively, e.g. by injecting hydrocarbon into the exhaust system upstreamof the filter, wherein the zeolite catalyst for use in the presentinvention is located downstream of the filter.

According to another aspect of the invention, provided is a method forthe reduction of NOx compounds and/or oxidation of NH₃ in a gas, whichcomprises contacting the gas with JMZ-5C, a metal impregnated JMZ-5C,JMZ-6C or a metal impregnated JMZ-6C for a time sufficient to reduce thelevel of NO_(x) compounds in the gas. Methods of the treating theexhaust gas may comprise one or more of the following steps: (a)accumulating and/or combusting soot that is in contact with the inlet ofa catalytic filter; (b) introducing a nitrogenous reducing agent intothe exhaust gas stream prior to contacting the catalytic filter,preferably with no intervening catalytic steps involving the treatmentof NO_(x) and the reductant; (c) generating NH₃ over a NO_(x) adsorbercatalyst or lean NO_(x) trap, and preferably using such NH₃ as areductant in a downstream SCR reaction; (d) contacting the exhaust gasstream with a DOC to oxidize hydrocarbon based soluble organic fraction(SOF) and/or carbon monoxide into CO₂, and/or oxidize NO into NO₂, whichin turn, may be used to oxidize particulate matter in particulatefilter; and/or reduce the particulate matter (PM) in the exhaust gas;(e) contacting the exhaust gas with one or more flow-through SCRcatalyst device(s) in the presence of a reducing agent to reduce the NOxconcentration in the exhaust gas; and (f) contacting the exhaust gaswith an ammonia slip catalyst, preferably downstream of the SCR catalystto oxidize most, if not all, of the ammonia prior to emitting theexhaust gas into the atmosphere or passing the exhaust gas through arecirculation loop prior to exhaust gas entering/re-entering the engine.

All, or at least a portion of, the nitrogen-based reductant,particularly NH₃, for consumption in the SCR process can be supplied bya NOx adsorber catalyst (NAC), a lean NOx trap (LNT), or a NOxstorage/reduction catalyst (NSRC), disposed upstream of the SCRcatalyst, e.g., a SCR catalyst of the present invention disposed on awall-flow filter. NAC components useful in the present invention includea catalyst combination of a basic material (such as alkali metal,alkaline earth metal or a rare earth metal, including oxides of alkalimetals, oxides of alkaline earth metals, and combinations thereof), anda precious metal (such as platinum), and optionally a reduction catalystcomponent, such as rhodium. Specific types of basic material useful inthe NAC include cesium oxide, potassium oxide, magnesium oxide, sodiumoxide, calcium oxide, strontium oxide, barium oxide, and combinationsthereof. The precious metal is preferably present at about 10 to about200 g/ft³, such as 20 to 60 g/ft³. Alternatively, the precious metal ofthe catalyst is characterized by the average concentration which may befrom about 40 to about 100 grams/ft³.

During periodically rich regeneration events, NH₃ may be generated overa NO_(x) adsorber catalyst. The SCR catalyst downstream of the NO_(x)adsorber catalyst may improve the overall system NO_(x) reductionefficiency. In the combined system, the SCR catalyst is capable ofstoring the released NH₃ from the NAC catalyst during rich regenerationevents and utilizes the stored NH₃ to selectively reduce some or all ofthe NO_(x) that slips through the NAC catalyst during the normal leanoperation conditions.

The method for treating exhaust gas as described herein can be performedon an exhaust gas derived from a combustion process, such as from aninternal combustion engine (whether mobile or stationary), a gas turbineand coal or oil fired power plants. The method may also be used to treatgas from industrial processes such as refining, from refinery heatersand boilers, furnaces, the chemical processing industry, coke ovens,municipal waste plants and incinerators, etc. The method can be used fortreating exhaust gas from a vehicular lean burn internal combustionengine, such as a diesel engine, a lean-burn gasoline engine or anengine powered by liquid petroleum gas or natural gas.

In certain aspects, the invention is a system for treating exhaust gasgenerated by combustion process, such as from an internal combustionengine (whether mobile or stationary), a gas turbine, coal or oil firedpower plants, and the like. Such systems include a catalytic articlecomprising JMZ-5C, described herein, and at least one additionalcomponent for treating the exhaust gas, wherein the catalytic articleand at least one additional component are designed to function as acoherent unit.

A system can comprise a catalytic article comprising one or more ofJMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metal impregnatedJMZ-6C; a conduit for directing a flowing exhaust gas; and a source ofnitrogenous reductant disposed upstream of the catalytic article. Thesystem can include a controller for metering the nitrogenous reductantinto the flowing exhaust gas only when it is determined that JMZ-5C or ametal containing JMZ-5C is capable of catalyzing NO_(x) reduction at orabove a desired efficiency over a specific temperature range, such as atabove 100° C., above 150° C. or above 175° C. The metering of thenitrogenous reductant can be arranged such that 60% to 200% oftheoretical ammonia is present in exhaust gas entering the SCR catalystcalculated at 1:1 NH₃/NO and 4:3 NH₃/NO₂.

The system can comprise an oxidation catalyst (e.g., a diesel oxidationcatalyst (DOC)) for oxidizing nitrogen monoxide in the exhaust gas tonitrogen dioxide can be located upstream of a point of metering thenitrogenous reductant into the exhaust gas. The oxidation catalyst canbe adapted to yield a gas stream entering the SCR zeolite catalysthaving a ratio of NO to NO₂ of from about 4:1 to about 1:3 by volume,e.g. at an exhaust gas temperature at oxidation catalyst inlet of 250°C. to 450° C. The oxidation catalyst can include at least one platinumgroup metal (or some combination of these), such as platinum, palladium,or rhodium, coated on a flow-through monolith substrate. The at leastone platinum group metal can be platinum, palladium or a combination ofboth platinum and palladium. The platinum group metal can be supportedon a high surface area washcoat component such as alumina, a zeolitesuch as an aluminosilicate zeolite, silica, non-zeolite silica alumina,ceria, zirconia, titania or a mixed or composite oxide containing bothceria and zirconia.

A suitable filter substrate can be located between the oxidationcatalyst and the SCR catalyst. Filter substrates can be selected fromany of those mentioned above, e.g. wall flow filters. Where the filteris catalyzed, e.g. with an oxidation catalyst of the kind discussedabove, preferably the point of metering nitrogenous reductant is locatedbetween the filter and the zeolite catalyst. Alternatively, if thefilter is un-catalyzed, the means for metering nitrogenous reductant canbe located between the oxidation catalyst and the filter.

In another aspect of the invention, JMZ-5C, a metal impregnated JMZ-5C,JMZ-6C or a metal impregnated JMZ-6C can promote the formation ofmethylamines from reaction of methanol and ammonia.

In another aspect of the invention, provided is a method of convertingan oxygenate, such as methanol, to an olefin (MTO) by contactingmethanol with a calcined molecular sieve of the first aspect of theinvention. The reaction process for the conversion of an oxygenate toolefin (OTO) is well known in the art. Specifically, in an OTO reactionprocess, an oxygenate contacts a molecular sieve catalyst compositionunder conditions effective to convert at least a portion of theoxygenate to light olefins. When methanol is the oxygenate, the processis generally referred to as a methanol to olefin (MTO) reaction process.Methanol is a particularly preferred oxygenate for the synthesis ofethylene and/or propylene. A process for converting an oxygenate feed toa light olefin product comprises: a) providing an oxygenate feedcomprising a majority of methanol; b) providing a catalyst compositioncomprising JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metalimpregnated JMZ-6C and optionally a basic metal oxide co-catalyst; andc) contacting the oxygenate feed with the catalyst composition underconditions sufficient to convert at least a portion of the oxygenatefeed to a light olefin product.

An oxygenate feedstock, particularly a mixed alcohol compositioncontaining methanol and ethanol, is a useful feedstock for a variety ofcatalytic processes, particularly oxygenate to olefin (OTO) reactionprocesses, in which a catalyst composition, typically containing aprimary oxide catalyst having at least two of Al, Si, and P (e.g., analuminosilicate molecular sieve, preferably a high-silicaaluminosilicate molecular sieve) and preferably a basic metal oxideco-catalyst, can be used to convert the oxygenate feedstock into a lightolefin product, e.g., containing ethylene and/or propylene, preferablyincluding ethylene. The olefins can then be recovered and used forfurther processing, e.g., in the manufacture of polyolefins such aspolyethylene and/or polypropylene, olefin oligomers, olefin copolymers,mixtures thereof, and/or blends thereof.

One or more additional components can be included in the feedstock thatis directed to the OTO reaction system. For example, a feedstockdirected to the OTO reaction system can optionally contain, in additionto methanol and ethanol, one or more aliphatic-containing compounds suchas alcohols, amines, carbonyl compounds for example aldehydes, ketonesand carboxylic acids, ethers, halides, mercaptans, sulfides, and thelike, and mixtures thereof. The aliphatic moiety of thealiphatic-containing compounds typically contains from 1 to 50 carbonatoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to10 carbon atoms, most preferably from 1 to 4 carbon atoms.

Non-limiting examples of aliphatic-containing compounds include:alcohols such as methanol, ethanol, n-propanol, isopropanol, and thelike, alkyl-mercaptans such as methyl mercaptan and ethyl mercaptan,alkyl-sulfides such as methyl sulfide, alkyl amines such as methylamine, alkyl ethers such as DME, diethyl ether and methyl ethyl ether,alkyl-halides such as methyl chloride and ethyl chloride, alkyl ketonessuch as dimethyl ketone, alkyl-aldehydes such as formaldehyde andacetaldehyde, and various organic acids such as formic acid and aceticacid.

The various feedstocks discussed above are converted primarily into oneor more olefins. The olefins or olefin monomers produced from thefeedstock typically have from 2 to 30 carbon atoms, preferably 2 to 8carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably2 to 4 carbons atoms, and most preferably ethylene and/or propylene.Non-limiting examples of olefin monomer(s) include ethylene, propylene,butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1,preferably ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,hexene-1, octene-1 and isomers thereof. Other olefin monomers caninclude, but are not limited to, unsaturated monomers, diolefins having4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes,vinyl monomers, and cyclic olefins.

A catalyst article for converting a low molecular weight oxygencontaining species to an olefin rich hydrocarbon stream can compriseJMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metal impregnatedJMZ-6C, where one or more of these catalysts is disposed on a supportand/or within a structure.

A catalyst article for converting a low molecular weight oxygencontaining species to an aromatic rich hydrocarbon stream can compriseJMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or a metal impregnatedJMZ-6C, where one or more of these catalysts is disposed on a supportand/or within a structure.

The catalyst can be incorporated or mixed with other additive materials.Such an admixture is typically referred to as formulated catalyst or ascatalyst composition. Preferably, the additive materials aresubstantially inert to conversion reactions involving dialkyl ethers(e.g., dimethyl ether) and/or alkanols (e.g., methanol, ethanol, and thelike).

One or more other materials can be mixed with JMZ-5C, a metalimpregnated JMZ-5C, JMZ-6C or a metal impregnated JMZ-6C, particularly amaterial that is resistant to the temperatures and other conditionsemployed in organic conversion processes. Such materials can includecatalytically active and inactive materials and synthetic or naturallyoccurring zeolites, as well as inorganic materials such as clays,silica, and/or other metal oxides such as alumina. The latter may beeither naturally occurring or in the form of gelatinous precipitates orgels including mixtures of silica and metal oxides. Use of acatalytically active material can tend to change the conversion and/orselectivity of the catalyst in the oxygenate conversion process.Inactive materials suitably can serve as diluents to control the amountof conversion in the process so that products can be obtained in aneconomic and orderly manner without employing other means forcontrolling the rate of reaction. These materials can be incorporatedinto naturally occurring clays, e.g., bentonite and kaolin, to improvethe crush strength of the catalyst under commercial operatingconditions. The materials (e.g., clays, oxides, etc.) can function asbinders for the catalyst. It can be desirable to provide a catalysthaving good crush strength, because, in commercial use, it can bedesirable to prevent the catalyst from breaking down into powder-likematerials.

Naturally occurring clays that can be employed can include, but are notlimited to, the montmorillonite and kaolin family, which familiesinclude the subbentonites, and the kaolins commonly known as Dixie,McNamee, Georgia and Florida clays, or others in which the main mineralconstituent includes halloysite, kaolinite, dickite, nacrite, oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment, or chemicalmodification. Other useful binders can include, but are not limited to,inorganic oxides such as silica, titanic, beryllia, alumina, andmixtures thereof.

In addition to the foregoing materials, JMZ-5C, a metal impregnatedJMZ-5C, JMZ-6C or a metal impregnated JMZ-6C can be composited with aporous matrix material such as silica-alumina, silica-magnesia,silica-zirconia, silica-thoria, silica-beryllia and silica-titania aswell as ternary compositions such as silica-alumina-thoria,silica-alumina-zirconia, silica-alumina-magnesia andsilica-magnesia-zirconia.

The relative proportions of JMZ-5C, a metal impregnated JMZ-5C, JMZ-6Cor a metal impregnated JMZ-6C and an inorganic oxide matrix can varywidely. For example, a mixture can include a zeolite content rangingfrom about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange from about 2 to about 80 weight percent of the composite.

The invention also relates to C2, C3, C4 and C5 products formed by OTOor MTO application using JMZ-5C, a metal impregnated JMZ-5C, JMZ-6C or ametal impregnated JMZ-6C as a catalyst or co-catalyst.

EXAMPLES

Materials produced in the examples described below were characterized byone or more of the following analytic methods. Powder X-ray diffraction(PXRD) patterns were collected on a X′pert powder diffactometer(Philips) using a CuKα radiation (45 kV, 40 mA) at a step size of 0.04°and a 1 s per step between 5° and 40° (2θ). Scanning electron microscopy(SEM) images and chemical compositions by energy-dispersive X-rayspectroscopy (EDX) were obtained on a JSM7400F microscope (JEOL) with anaccelerating voltage of 3-10 KeV. The micropore volume and surface areawere measured using N2 at 77 K on a 3Flex surface characterizationanalyzer (Micrometrics).

Example 1 Synthesis of SZR

SZR zeolite was prepared by the hydrothermal technique similar to thatreported in Gao, S.; Wang, X.; Chu, W. The first study on the synthesisof uniform SUZ-4 zeolite nanofiber. Microporous and Mesoporous Materials2012, 159, 105-110.

An aluminosilicate gel having a molar composition:

21.22 SiO₂: Al₂O₃: 7.9 KOH: 2.6 TEAOH:498.6 H₂O

was prepared by first dissolving 1.19 g of KOH pellet (85 wt %) in 14.37g of deionized water. 0.12 g of Al powder was added to the stirredsolution. After complete dissolution of Al powder, another solutioncontaining 7.29 g Ludox AS-40, and 2.5 g tetraethylammounium hydroxide(25 wt %) was added to the mixture and stirring was continued for 3 h oruntil a homogeneous gel was obtained. The resulting aluminosilicate gelwas then transferred to an autoclave reactor and reacted at 150° C.under 45 rpm rotation for 4 days. The reaction mixture had asilicon:aluminum ratio of 10.6.

The oven was cooled, the reactor was opened and the resulting materialwas separated by filtration, with the addition of de-mineralised water.After the initial mixing with water and the removal of the water, theprocedure was repeated two additional times (three washes in total)following which resulting product was dried overnight at 80° C. and theas-made product was formed. A sample of the as-made product was calcinedby heating the sample from room temperature to 150° C. at a 1 C/minheating rate, holding the sample at 150° C. for 3 h, increasing thetemperature to 550° C. at a heating rate of 1° C/min and maintaining thetemperature at 550° C. for 6 h.

Samples of the dried product were analysed by XRD and SEM as describedabove. Analysis of the both the as-made and calcined products by powderXRD (FIG. 3) indicated that both of these products had an SZR structurewhen compared to values in the literature. An SEM of the calcinedproduct (FIG. 4) showed that the material had a needle-like morphology,as was known for SUZ-4. The product had a BET surfaces area of 299 m²/gand a pore volume of 0.13 cm³/g.

Example 2 Synthesis of JMZ-5 Using Faujasite as the Source of Siliconand Aluminum

The procedure in Example 1 was changed by replacing Ludox AS-40 and Almetal powder as the silica and aluminum sources with commerciallyavailable faujasite zeolite having an SAR of 30 (CBV 720, Zeolyst). SEMof the faujasite is shown in FIG. 5. The reaction gel had a compositionof:

30 SiO₂:Al₂O₃: 11.2 KOH: 3.7 TEAOH: 704.9 H₂O.

The reaction mixture had a silicon:aluminum ratio of 15. The reactiongel was reacted for 4 days.

Analysis of the dried powder by powder XRD (FIG. 6) indicated that theproduct was had an SZR crystal structure. SEM of the calcined powder(FIG. 7) showed that the product (JMZ-5) had a sea-urchin morphology.

Example 3 Synthesis of JMZ-5 Using Calcined Aluminosilicate CHA Seeds

The procedure in Example 1 was modified by the addition of calcinedaluminosilicate CHA seeds (5 wt % of the total amount of silica in thereaction mixture (not including the seeds) to the reaction mixture afterall of the other components had been added. SEM of the calcinedaluminosilicate CHA seeds is shown in FIG. 8. The final reaction gel hada composition of:

21.22 SiO₂:Al₂O₃: 7.9 KOH: 2.6 TEAOH: 498.6 H₂O+ calcined CHA seeds.

The reaction gel was reacted for 8 days.

Analysis of the dried product by powder XRD (FIG. 9) indicated that theproduct had SZR crystal structure. SEM of the calcined powder shows thatthe material produced using calcined aluminosilicate seeds had seaurchin morphology (FIG. 10), as was JMZ-5.

FIG. 11 shows the XRD and SEM spectra of JMZ-5 made using CHA seeds,JMZ-5 made using FAU as the source of silicon and aluminium and SZR. TheXRD spectra of JMZ-5 contains the same peaks as SZR, but the SEMs showthat the morphology of JMZ-5 (sea urchin type) is distinct from that ofSZR (needles)

Example 4 Synthesis of JMZ-5 Using Calcined Silica CHA Seed

The procedure in Example 3 was modified by the addition of pure silicaCHA seeds in place of the calcined aluminosilicate CHA seeds. An SEM ofthe pure silica CHA seeds is shown in FIG. 12.

Analysis of the dried powder by powder XRD (FIG. 13) indicated that theproduct was not in a pure SZR phase, but also contained peakscorresponding to a CHA crystal structure. SEM of the powder shows thatthe material produced using calcined pure silica CHA seeds had acicular(sea urchin like) morphology. (FIG. 14)

Example 5 Attempted Synthesis of JMZ-5 Using FAU Seeds

The procedure in Example 3 was modified by the addition of FAU seeds inplace of the calcined aluminosilicate CHA seeds.

Analysis of the as-made dried powder by powder XRD (FIG. 15) indicatedthat the product was amorphous and did not have a crystal structure.

Example 6 Attempted Synthesis of JMZ-5 Using as-Made (3-Zeolite (BEA)Seeds

The procedure in Example 3 was modified by the addition of as-made boronzeolite Beta seeds in place of the calcined aluminosilicate CHA seeds.

Analysis of the as-made and calcined dried powders by powder XRD (FIG.16) indicated that the product had the BEA crystal structure, not theSZR crystal structure.

Example 7 Attempted Synthesis of JMZ-5 Using Calcined Aluminosilicate(3-Zeolite (BEA) Seeds

The procedure in Example 3 was modified by the addition of calcinedaluminosilicate β-zeolite (BEA) seeds in place of the calcinedaluminosilicate CHA seeds.

Analysis of the as-made and calcined dried powders by powder XRD (FIG.17) indicated that the product had the BEA crystal structure, not theSZR crystal structure.

Example 8 Attempted Synthesis of JMZ-5 Using as-Made Pure Silica LTASeeds

The procedure in Example 3 was modified by the addition of as-made puresilica LTA seeds in place of the calcined aluminosilicate CHA seeds.

Analysis of the as-made dried powder by powder XRD (FIG. 18) indicatedthat the product had SZR crystal structure. SEM of the powder shows thatthe as-made material produced using as-made silica LTA seeds hadneedle-like morphology and therefore did not produce JMZ-5 or JMZ-6.(FIG. 19)

Example 9 Synthesis of JMZ-5 Using Calcined Silica LTA Seeds

The procedure in Example 3 was modified by the addition of calcinedsilica LTA seeds in place of the calcined aluminosilicate CHA seeds.

Analysis of the as-made dried powder by powder XRD (FIG. 20) indicatedthat the product had SZR crystal structure. SEM of the calcined powdershows that the material produced using calcined silica LTA seeds had seaurchin morphology. (FIG. 21)

Example 10 Synthesis of JMZ-6 Using as-Made Aluminosilicate LTA Seeds

The procedure in Example 3 was modified by the addition of as-madealuminosilicate LTA seeds in place of the calcined aluminosilicate CHAseeds.

Analysis of the as-made dried powder by powder XRD (FIG. 22) indicatedthat the product had SZR crystal structure. SEM of the calcined powdershows that the material produced using as-made aluminosilicate LTA seedshad a needle-aggregates morphology. (FIG. 23)

Example 11 Synthesis of JMZ-5 Using Calcined Aluminosilicate LTA Seeds

The procedure in Example 3 was modified by the addition of calcinedaluminosilicate LTA seeds in place of the calcined aluminosilicate CHAseeds.

Analysis of the as-made dried powder by powder XRD (FIG. 24) indicatedthat the product had SZR crystal structure. SEM of the calcined powdershows that the material produced using calcined aluminosilicate LTAseeds had sea urchin morphology. (FIG. 25)

Example 12 Catalyst Testing for NH₃ SCR

Calcined JMZ-5 product, JMZ-5C, was impregnated with copper at a loadingof 3 wt % using the required amount of copper (II) acetate monohydrate(Alfa Aesar) dissolved in de-mineralised water. The impregnated samplewas dried overnight at 105° C. and then calcined in air at 500° C. for 2hours.

Similar samples were prepared using AEI and BEA.

Samples of the powdered catalyst were pelletized and then aged in a flowof 4.5% H₂O in air. The samples were heated at a rate of 10° C./min to900° C. After being held at a temperature of 900° C. for either 1 or 3hours, the samples were cooled in the steam/air mixture until thentemperature was <200° C., then air only flowed over the samples untilthey cooled to about room temperature.

Pelletized samples of the powder catalyst were tested in an apparatus inwhich a gas comprising 500 ppm NOx (NO-only), 550 ppm NH_(3, 10)%O₂, 10%H₂O, with the remainder being N₂ flowed over the catalyst at a spacevelocity of 60K (390L/gcat/h). The temperature was increased (ramped)from 150 to 500° C. at 5° C./minute.

Fresh and aged NOx conversion activity profiles over temperatures fromabout 150° C. to about 500° C. are given in FIGS. 26 and 28 (fresh, aged1 hour and aged 3 hours, respectively). The activity of fresh samples ofJMZ-5 had a higher T50 (the temperature for 50% conversion) than the AEIand BEA samples. The aged samples of JMZ-5 and BEA showed a decrease inNOx conversion, with BEA being most affected by aging. Both of the JMZ-5samples had levels of NOx conversion greater than that of BEA atstarting at temperatures of about 200-250° C. At temperatures aboveabout 250° C., the amount of NOx conversion was about 15-25% higher thanthat from the BEA samples.

The concentration of N₂O in gas passing through fresh and aged catalystsover temperatures from about 150° C. to about 500° C. are given in FIGS.28 and 29 (fresh, aged 1 hour and aged 3 hours, respectively). Gasflowing into the apparatus contained 500 ppm NOx as NO-only. In thefresh samples, the levels of N₂O in gas after passing through the AEIcatalyst were the lowest, with JMZ-5 samples made with CHA seeds providethe next lowest N₂O levels. N₂O levels from the JMZ-5 samples made withFAU source provide N₂O levels that were similar to those from BEA,except the peaks level in this JMZ-5 sample occurred at about 20° C.higher. In the aged samples, AEI produced the highest levels. Thisappears to be related to the much higher NOx conversion from thissample. The two JMZ-5 samples produced less N₂O than BEA at temperaturesfrom about 200-300 C and above 400 C, and comparable amount of N₂O asfrom BEA from about 300-400° C.

This shows that both JMZ-5 samples had delayed fresh lightoff,selectivity similar to BEA, and improved durability relative to BEA.

What is claimed is:
 1. An aluminosilicate molecular sieve comprising anSZR type framework and having acicular type morphology (JMZ-5) orneedle-aggregate type morphology (JMZ-6).
 2. The aluminosilicatemolecular sieve of claim 1, having an X-ray powder diffraction patternsubstantially similar to that of an SZR type framework.
 3. Thealuminosilicate molecular sieve of claims 1, where the molecular sievehas a silica to alumina ratio (SAR) of 15 to 40-when the molecular sievehas an acicular type morphology or a silica to alumina ratio (SAR) of 10to 30-when the molecular sieve has a needle-aggregate type morphology.4. The aluminosilicate molecular sieve of claim 1, where thealuminosilicate molecular sieve further comprises a structure-directingagent, preferably comprising tetraethylammonium cations, N′, N′, N′, N′,N′, N′-hexaethylpentanediammonium cations or quinuclidine.
 5. A calcinedaluminosilicate molecular sieve comprising a SZR type framework andhaving a sea-urchin type crystal morphology (JMZ-5) or a needleaggregate type morphology (JMZ-6).
 6. The calcined aluminosilicatemolecular sieve of claim 5, wherein the calcined aluminosilicatemolecular sieve further comprises an extra-framework metal, wherein theextra-framework metal is an alkali metal, an alkaline earth metal, atransition metal or a mixture thereof.
 7. The calcined aluminosilicatemolecular sieve of claim 6, where the extra-framework metal comprisescalcium, cerium, cobalt, copper, chromium, iron, lithium, manganese,nickel, potassium, sodium, strontium or a combination of two or more ofthese metals.
 8. A catalyst composition comprising a calcinedaluminosilicate molecular sieve of claim
 5. 9. The catalyst compositionof claim 8, wherein the catalyst further comprises an extra-frameworkmetal wherein the extra-framework metal comprises an alkali metal, analkaline earth metal, a transition metal or a mixture thereof.
 10. Thecatalyst composition of claim 9, wherein the extra-framework metal iscalcium, cerium, cobalt, copper, chromium, iron, lithium, manganese,molybdenum, nickel, niobium, potassium, sodium, strontium, tantalum,tungsten, or vanadium or a combination of two or more of these metals.11. The catalyst composition of claim 9, wherein the extra-frameworkmetal comprises about 0.1 to about 10, preferably about 0.1 to about 5,weight percent of total weight of the molecular sieves, extra-frameworkmetal and catalytically active metal in the catalyst a transition metalor noble metal.
 12. The catalyst composition of claim 10, wherein themolecular sieve comprises about 0.1 to about 10, preferably about 0.1 toabout 5, weight percent of copper, iron, manganese or a combination oftwo or more of these metals.
 13. A catalyst article for treating exhaustgas, the catalyst article comprising a calcined aluminosilicatemolecular sieve of 5, where the calcined aluminosilicate molecular sieveis disposed on and/or within a substrate, preferably a honeycombsubstrate.
 14. A method for synthesizing an aluminosilicate molecularsieve of claim 1, the method comprising: a. forming a reaction mixturecomprising: (a) a source of silicon and aluminum, where the source ofboth silicon and aluminum is an aluminosilicate molecular sieve having anon-SZR type structure, and (b) a structure directing agent (SDA)comprising a tetraethylammonium cation, b. forming crystals comprisingan SZR type framework and the structure directing agent byhydrothermally aging the reaction mixture formed in step a, and c.recovering at least a portion of the molecular sieve crystals from themother liquor, where the molecular sieve crystals comprise JMZ-5. 15.The method of claim 14, wherein the source of silicon and/or aluminumfurther comprises one or more additional components, wherein the one ormore additional components are present in an amount such that at least80% of the silicon and/or aluminum in the reaction mixture is providedby the aluminosilicate molecular sieve which does not have the SZR typestructure.
 16. The method of claim 14, wherein the molecular sieve thatis the source of alumina and silica is one or more of faujasite (FAU),mordenite (MOR), zeolite P (GIS), and zeolite A (LTA).
 17. The method ofclaim 14, wherein the SDA is associated with an anion selected from thegroup consisting of fluoride, chloride, bromide, iodide, hydroxide,acetate, sulfate, tetrafluoroborate, carboxylate, carbonate andbicarbonate, and nitrate.
 18. The method of claim 14, wherein thereaction mixture is essentially free of fluoride.
 19. The method ofclaim 14, wherein the reaction mixture further comprises a source ofalkali or alkaline earth metal (M), wherein the weight ratio of SiO₂:MxOy (oxide of the alkali or alkaline earth metal) is from 2 to 10,where M=Na, K, Ca, or Sr, and mixtures thereof.
 20. The method of claim14, wherein the reaction mixture further comprises a source ofpotassium.
 21. The method of claim 14, wherein the reaction mixture is agel having a molar compositional ratio of: H₂O/SiO₂  10-100 OH⁻/SiO₂0.01-1  R/SiO₂ 0.05-0.5 Al₂O₃/SiO₂ 0.01-0.1

wherein R is the SDA.
 22. A method for synthesizing an aluminosilicatemolecular sieve of claim 1, the method comprising: a. forming a reactionmixture comprising: (a) at least one source of alumina, (b) at least onesource of silica, and (c) a structure directing agent (SDA) comprisingtetraethylammonium cations, N′, N′, N′, N′, N′,N′-hexaethylpentanediammonium cations or quinuclidine, b. addingcalcined aluminosilicate molecular sieve seed crystals to the reactionmixture where the calcined aluminosilicate molecular sieve seed crystalsare a non-SZR type, c. forming crystals comprising an SZR type frameworkand the structure directing agent, and d. recovering at least a portionof the molecular sieve crystals from the mother liquor, where themolecular sieve crystals comprise JMZ-5.
 23. The method of claim 22,where the calcined aluminosilicate molecular sieve seed crystalscomprise one or more of calcined Al-CHA, calcined silica LTA, calcinedAl-LTA.
 24. A method for synthesizing an aluminosilicate molecular sieveof claim 1, the method comprising: a. forming a reaction mixturecomprising: (a) at least one source of alumina, (b) at least one sourceof silica, and (c) a structure directing agent (SDA) comprisingtetraethylammonium cations, N′, N′, N′, N′, N′,N′-hexaethylpentanediammonium cations or quinuclidine, b. adding as-madealuminosilicate seed crystals having an LTA type framework to thereaction mixture, c. forming crystals comprising an SZR type frameworkand the structure directing agent, and d. recovering at least a portionof the molecular sieve crystals from the mother liquor, where themolecular sieve crystals are JMZ-6.
 25. A method for treating an exhaustgas comprising contacting a combustion exhaust gas containing NO_(x)and/or NH₃ with a catalyst article of claim
 13. 26. The method of claim25, wherein the method selectively reduces at least a portion of theNO_(x) into N₂ and H₂O and/or oxidize at least a portion of the NH₃.